Synergistic pesticidal mixtures

ABSTRACT

Synergistic pesticidal mixtures are provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This applications claims priority from U.S. Provisional application60/927,119 filed on May 1, 2007, the entire disclosure of which ishereby incorporated by reference.

FIELD OF THE INVENTION

The invention disclosed in this document is related to field ofpesticides and their use in controlling pests.

BACKGROUND OF THE INVENTION

Pests cause millions of human deaths around the world each year.Furthermore, there are more than ten thousand species of pests thatcause losses in agriculture. These agricultural losses amount tobillions of U.S. dollars each year. Termites cause damage to variousstructures such as homes. These termite damage losses amount to billionsof U.S. dollars each year. As final note, many stored food pests eat andadulterate stored food. These stored food losses amount to billions ofU.S. dollars each year, but more importantly, deprive people of neededfood.

There is an acute need for new pesticides. Insects are developingresistance to pesticides in current use. Hundreds of insect species areresistant to one or more pesticides. The development of resistance tosome of the older pesticides, such as DDT, the carbamates, and theorganophosphates, is well known. But resistance has even developed tosome of the newer pesticides. Therefore, a need exists for newpesticides and particularly for pesticides that have new modes ofaction.

SUBSTITUENTS (NON-EXHAUSTIVE LIST)

The examples given for the substituents are (except for halo)non-exhaustive and must not be construed as limiting the inventiondisclosed in this document.

“alkoxy” means an alkyl further consisting of a carbon-oxygen singlebond, for example, methoxy, ethoxy, propoxy, isopropoxy, 1-butoxy,2-butoxy, isobutoxy, tert-butoxy, pentoxy, 2-methylbutoxy,1,1-dimethylpropoxy, hexoxy, heptoxy, octoxy, nonoxy, and decoxy.

“alkyl” means an acyclic, saturated, branched or unbranched, substituentconsisting of carbon and hydrogen, for example, methyl, ethyl, propyl,isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl,2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, anddecyl.

“halo” means fluoro, chloro, bromo, and iodo.

“haloalkyl” means an alkyl further consisting of, from one to themaximum possible number of, identical or different, halos, for example,fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoromethyl,2-fluoroethyl, 2,2,2-trifluoroethyl, chloromethyl, trichloromethyl, and1,1,2,2-tetrafluoroethyl.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of the following formula are synergistic with a variety ofother pesticides.

wherein

X represents NO₂, CN or COOR⁴;

L represents a single bond or R¹, S and L taken together represent a 5-or 6-membered ring;

R¹ represents methyl or ethyl;

R² and R³ independently represent hydrogen, methyl, ethyl, fluoro,chloro or bromo;

n is an integer from 0-3;

Y represents 6-halopyridin-3-yl, 6-(C₁-C₄)alkylpyridin-3-yl,6-halo(C₁-C₄)alkylpyridin-3-yl, 6-(C₁-C₄)alkoxypyridin-3-yl,6-halo(C₁-C₄)alkoxypyridin-3-yl, 2-chlorothiazol-4-yl, or3-chloroisoxazol-5-yl when n=0-3 and L represents a single bond, or Yrepresents hydrogen, C₁-C₄ alkyl, phenyl, 6-halopyridin-3-yl,6-(C₁-C₄)alkylpyridin-3-yl, 6-halo(C₁-C₄)alkylpyridin-3-yl,6-(C₁-C₄)alkoxypyridin-3-yl, 6-halo(C₁-C₄)alkoxypyridin-3-yl,2-chlorothiazol-4-yl, or 3-chloroisoxazol-5-yl when n=0-1 and R¹, S andL taken together represent a 5- or 6-membered ring; and

R⁴ represents C₁-C₃ alkyl.

Methods for the preparation of sulfoximines, other than those describedin Scheme H, have been previously disclosed in US Patent Publication20050228027, whose teachings are incorporated herein.

The compounds of formula (Ia), wherein R¹, R², R³, R⁴, X, and Y are aspreviously defined and L is a single bond, can be prepared by themethods illustrated in Scheme A:

In step a of Scheme A, sulfide of formula (A) is oxidized withmeta-chloroperoxybenzoic acid (mCPBA) in a polar solvent below 0° C. toprovide sulfoxide of formula (B). In most cases, dichloromethane is thepreferred solvent for oxidation.

In step b of Scheme A, sulfoxide (B) is iminated with sodium azide inthe presence of concentrated sulfuric acid in an aprotic solvent underheating to provide sulfoximine of formula (C). In most cases, chloroformis the preferred solvent for this reaction.

In step c of Scheme A, the nitrogen of sulfoximine (C) can be eithercyanated with cyanogen bromide in the presence of a base, or nitratedwith nitric acid in the presence of acetic anhydride under mildlyelevated temperature, or carboxylated with alkyl (R⁴) chloroformate inthe presence of base such as 4-dimethylaminopyridine (DMAP) to provideN-substituted sulfoximine (Ia). Base is required for efficient cyanationand carboxylation and the preferred base is DMAP, whereas sulfuric acidis used as catalyst for efficient nitration reaction.

The compounds of formula (Ia), wherein X represents CN and R¹, R², R³,R⁴ and Y are as previously defined, can be prepared by the mild andefficient method illustrated in Scheme B.

In step a of Scheme B, sulfide is oxidized with iodobenzene diacetate inthe presence of cyanamide at 0° C. to give sulfilimine (F). The reactioncan be carried out in a polar aprotic solvent like dichloromethane.

In step b of Scheme B, the sulfilimine (F) is oxidized with mCPBA. Abase such as potassium carbonate is employed to neutralize the acidityof mCPBA. Protic polar solvents such as ethanol and water are used toincrease the solubility of the sulfilimine starting material and thebase employed. The sulfilimine (F) can also be oxidized with aqueoussodium or potassium periodinate solution in the presence of catalystruthenium trichloride hydrate or similar catalyst. The organic solventfor this catalysis can be polar aprotic solvent such as dichloromethane,chloroform, or acetonitrile.

The α-carbon of the N-substituted sulfoximine of formula (Ia), i.e.,n=1, R³═H in the (CR²R³) group adjacent to the N-substituted sulfoximinefunction can be further alkylated or halogenated (R⁵) in the presence ofa base such as potassium hexamethyldisilamide (KHMDS) to giveN-substituted sulfoximines of formula (Ib), wherein R¹, R², R³, R⁴, X, Land Y are as previously defined and Z is an appropriate leaving group,as illustrated in Scheme C. The preferred leaving groups are iodide(R⁵=alkyl), benzenesulfonimide (R⁵═F), tetrachloroethene (R⁵═Cl), andtetrafluoroethene (R⁵═Br).

The starting sulfides (A) in Scheme A can be prepared in different waysas illustrated in Schemes D, E, F G, H, and I.

In Scheme D, the sulfide of formula (A₁), wherein R¹, R² and Y are aspreviously defined, n=1, and R³═H, can be prepared from the chloride offormula (D₁) by nucleophilic substitution with the sodium salt of analkyl thiol.

In Scheme E, the sulfide of formula (A₂), wherein R¹, R² and Y are aspreviously defined, n=3, and R³═H, can be prepared from the chloride offormula (D₂) by reacting with a 2-mono substituted methyl malonate inthe presence of base such as potassium tert-butoxide to provide2,2-disubstitued malonate, hydrolysis under basic conditions to form adiacid, decarboxylation of the diacid by heating to give a monoacid,reduction of the monoacid with borane-tetrahyrofuran complex to providean alcohol, tosylation of the alcohol with toluenesulfonyl chloride(tosyl chloride) in the presence of a base like pyridine to give atosylate and replacement of the tosylate with the sodium salt of thedesired thiol.

In Scheme F, the sulfide of formula (A₃), wherein R¹, R² and Y are aspreviously defined, n=2, and R³═H, can be prepared from the nitrile offormula (E) by deprotonation with a strong base and alkylation with analkyl iodide to give α-alkylated nitrile, hydrolysis of the α-alkylatednitrile in the presence of a strong acid like HCl to give an acid,reduction of the acid with borane-tetrahydrofuran complex to provide analcohol, tosylation of the alcohol with tosyl chloride in the presenceof a base like pyridine to give a tosylate and replacement of thetosylate with the sodium salt of the desired thiol.

In Scheme G, the sulfide of formula (A₄), wherein R¹, S and L takentogether form a ring, n=0, and Y=isopropyl or phenyl can be preparedfrom the unsubstituted cyclic sulfide wherein m=0, 1. Chlorination ofthe cyclic sulfide starting material with N-chlorosuccinimide in benzenefollowed by alkylation with Grignard reagent can lead to the desiredsulfide (A₄) in satisfactory yield.

An alternative method for the preparation of sulfides of formula (A₄),wherein R¹, S and L taken together form a ring, n=0, m=0, and Y=6-halo,6-(C₁-C₄)alkyl, 6-(C₁-C₄)haloalkyl or 6-(C₁-C₄)alkoxy substituted3-pyridyl is highlighted in Scheme H. Accordingly, the correspondingappropriately substituted chloromethyl pyridine is treated withthiourea, hydrolyzed and subsequently alkylated with1-bromo-3-chloropropane under aqueous base conditions, and cyclized inthe presence of a base like potassium tert-butoxide in a polar aproticsolvent such as tetrahydrofuran (THF).

In Scheme I, the sulfide of formula (A₅), wherein R¹ is previouslydefined, L is a bond, n=0 and Y is 6-chloropyridin-3-yl can be preparedfrom 2-chloro-5-bromopyridine with a halo-metal exchange followed by asubstitution with disulfide.

Sulfoximine compounds of type Ib wherein R¹, S and L taken together forma saturated 5- or 6-membered ring and n=1 can be prepared by the methodsillustrated in Scheme J wherein X and Y are as previously defined and mis 0 or 1.

In step a of Scheme J, which is similar to step b of Scheme A, sulfoxideis iminated with sodium azide in the presence of concentrated sulfuricacid or with O-mesitylsulfonylhydroxylamine in a polar aprotic solventto provide sulfoximine. Chloroform or dichloromethane are the preferredsolvents.

In step b of Scheme J, similar to step c of Scheme A, the nitrogen ofsulfoximine can be either cyanated with cyanogen bromide, or nitratedwith nitric acid followed by treatment with acetic anhydride underrefluxing conditions, or carboxylated with methyl chloroformate in thepresence of base such as DMAP to provide N-substituted cyclicsulfoximine. Base is required for efficient cyanation and carboxylationand the preferred base is DMAP, whereas sulfuric acid is used ascatalyst for efficient nitration reaction.

In step c of Scheme J, the α-carbon of N-substituted sulfoximine can bealkylated with a heteroaromatic methyl halide in the presence of a basesuch as KHMDS or butyl lithium (BuLi) to give the desired N-substitutedsulfoximines. The preferred halide can be bromide, chloride or iodide.

Alternatively, the compounds of formula (Ib) can be prepared by a firstα-alkylation of sulfoxides to give a-substituted sulfoxides and then animination of the sulfoxide followed by N-substitution of the resultingsulfoximine by using the steps c, a and b respectively as describedabove for Scheme J.

Compounds in which Y represents claimed substituents other than6-(C₁-C₄)haloalkylpyridin-3-yl and 6-(C₁-C₄)haloalkoxypyridin-3-yl havebeen disclosed in US Patent Publication 20050228027, whose teachings areincorporated herein.

Examples

The examples are for illustration purposes and are not to be construedas limiting the invention disclosed in this document to only theembodiments disclosed in these examples.

Example I[(6-Trifluoromethylpyridin-3-yl)methyl](methyl)-oxido-λ⁴-sulfanylidenecyanamide(1)

[(6-Trifluoromethylpyridin-3-yl)methyl](methyl)-oxido-λ⁴-sulfanylidenecyanamide(1) was prepared from 3-chloromethyl-6-(trifluoromethyl)pyridineaccording to the following three step sequence:

To a solution of 3-chloromethyl-6-(trifluoromethyl)pyridine (5.1 g, 26mmol) in dimethyl sulfoxide (DMSO; 20 mL) was added in one portionsodium thiomethoxide (1.8 g, 26 mmol). A violent exothermic reaction wasobserved which resulted in the reaction turning dark. The reaction wasstirred for 1 hr, then additional sodium thiomethoxide (0.91 g, 13 mmol)was added slowly. The reaction was stirred overnight, after which it waspoured into H₂O and several drops of conc. HCl were added. The mixturewas extracted with Et₂O (3×50 mL) and the organic layers combined,washed with brine, dried over MgSO₄ and concentrated. The crude productwas purified by chromatography (Prep 500, 10% acetone/hexanes) tofurnish the sulfide (A) as a pale yellow oil (3.6 g, 67%). ¹H NMR (300MHz, CDCl₃): δ 8.6 (s, 1H), 7.9 (d, 1H), 7.7 (d, 1H), 3.7 (s, 2H), 2.0(s, 3H); GC-MS: mass calcd for C₈H₈F₃NS [M]⁺ 207. Found 207.

To a solution of sulfide (A) (3.5 g, 17 mmol) and cyanamide (1.4 mg, 34mmol) in dichloromethane (30 mL) at 0° C. was added iodobenzenediacetate(11.0 g, 34 mmol) all at once. The reaction was stirred for 30 minutesthen allowed to warm to room temperature overnight. The mixture wasdiluted with dichloromethane (50 mL) and washed with H₂O. The aqueouslayer was extracted with ethyl acetate (4×50 mL), and the combineddichloromethane and ethyl acetate layers dried over MgSO₄ andconcentrated. The crude product was triturated with hexanes and purifiedby chromatography (chromatotron, 60% acetone/hexanes) to furnish thesulfilimine (B) as a yellow gum (0.60 g, 14%). IR (film) 3008, 2924,2143, 1693 cm⁻¹; ¹H NMR (300 MHz, CDCl₃): δ 8.8 (s, 1H), 8.0 (d, 1H),7.8 (d, 1H), 4.5 (d, 1H), 4.3 (d, 1H), 2.9 (s, 3H); LC-MS (ESI): masscalcd for C₉H₉F₃N₃S [M+H]⁺ 248.04. Found 248.

To a solution of m-chloroperbenzoic acid (mCPBA; 80%, 1.0 g, 4.9 mmol)in EtOH (10 mL) at 0° C. was added a solution of K₂CO₃ (1.4 g, 10 mmol)in H₂O (7 mL). The solution was stirred for 20 min and then a solutionof sulfilimine (B) (0.60 g, 2.4 mmol) in EtOH (20 mL) was added all atonce. The reaction was stirred at 0° C. for 30 min, and then allowed towarm to room temperature over the course of 1 hr. The reaction wasquenched with aq. sodium bisulfite and the mixture concentrated toremove ethanol. The resulting mixture was extracted with dichloromethaneand the combined organic layers dried over MgSO₄ and concentrated. Thecrude product was purified by chromatography (chromatotron, 50%acetone/hexanes) to furnish the sulfoximine (1) as an off-white solid(0.28 g, 44%). Mp=135-137° C.; ¹H NMR (300 MHz, CDCl₃): δ 8.8 (s, 1H),8.1 (d, 1H), 7.8 (d, 1H), 4.7 (m, 2H), 3.2 (s, 3H); LC-MS (ELSD): masscalcd for C₉H₉F₃N₃OS [M+H]⁺ 264.04. Found 263.92.

Example II1-(6-Trifluoromethylpyridin-3-yl)ethyl](methyl)-oxido-λ⁴-sulfanylidenecyanamide(2)

[1-(6-Trifluoromethylpyridin-3-yl)ethyl](methyl)-oxido-λ⁴-sulfanylidenecyanamide(2) was prepared from[(6-trifluoromethylpyridin-3-yl)methyl]-(methyl)-oxido-λ⁴-sulfanylidenecyanamide(1) using the method outlined in Scheme C:

To a solution of sulfoximine (1) (50 mg, 0.19 mmol) andhexamethylphosphoramide (HMPA; 17 μL, 0.10 mmol) in tetrahydrofuran(THF; 2 mL) at −78° C. was added potassium hexamethyldisilazane (KHMDS;0.5 M in toluene, 420 μL, 0.21 mmol) dropwise. The solution was stirredat −78° C. for an additional 20 min, after which iodomethane (13 μL,0.21 mmol) was added. The reaction was allowed to warm to roomtemperature over the course of 1 hr, after which it was quenched withsaturated aqueous (aq.) NH₄Cl and extracted with dichloromethane. Theorganic layer was dried over Na₂SO₄, concentrated, and the crude productpurified by chromatography (chromatotron, 70% acetone/CH₂Cl₂) to furnishthe sulfoximine (2) as a 2:1 mixture of diastereomers (colorless oil; 31mg, 59%). ¹H NMR (300 MHz, CDCl₃): δ (major diastereomer) 8.8 (s, 1H),8.1 (d, 1H), 7.8 (d, 1H), 4.6 (q, 1H), 3.0 (s, 3H), 2.0 (d, 3H); (minordiastereomer) 8.8 (s, 1H), 8.1 (d, 1H), 7.8 (d, 1H), 4.6 (q, 1H), 3.1(s, 3H), 2.0 (d, 3H); LC-MS (ELSD): mass calcd for C₁₀H₁₀F₃N₃OS [M+H]⁺278.06. Found 278.05.

Example III2-(6-Trifluoromethylpyridin-3-yl)-1-oxido-tetrahydro-1H-1λ⁴-thien-1-ylidenecyanamide(3)

2-(6-Trifluoromethylpyridin-3-yl)-1-oxido-tetrahydro-1H-14-thien-1-ylidene-cyanamide(3) was prepared from 3-chloromethyl-6-(trifluoromethyl)-pyridineaccording to the 5 step sequence outline below:

To a suspension of thiourea (1.2 g, 16 mmol) in EtOH (25 mL) was added asolution of 3-chloromethyl-6-(trifluoromethyl)pyridine in EtOH (10 mL).The suspension was stirred at room temperature for 2 days, during whicha white precipitated formed. The precipitate was filtered to give thedesired amidine hydrochloride as a white solid (2.4 g, 58%). Mp=186-188°C. No further attempt was made to purify the product. ¹H NMR (300 MHz,CDCl₃): δ 8.9 (bs, 4H), 8.4 (s, 1H), 7.6 (d, 1H), 7.3 (d, 1H), 4.2 (s,2H); LC-MS (ELSD): mass calcd for C₈H₈F₃N₃S [M+H]⁺ 236.05. Found 236.01.

To a solution of amidine hydrochloride (A) (1.8 g, 6.8 mmol) in H₂O (12mL) at 10° C. was added 10 N NaOH (0.68 mL, 6.8 mmol), which resulted inthe formation of a white precipitate. The suspension was heated at 100°C. for 30 min, then cooled back down to 10° C. Additional 10 N NaOH(0.68 mL, 6.8 mmol) was added, followed by 1-bromo-3-chloropropane (0.67mL, 6.8 mmol) all at once. The reaction was stirred at room temperatureovernight, then extracted with dichloromethane. The combined organiclayers were washed with brine, dried over Na₂SO₄ and concentrated tofurnish the sulfide (B) as a colorless oil (1.7 g, 96%). No furtherattempt was made to purify the product. ¹H NMR (300 MHz, CDCl₃): δ 8.6(s, 1H), 7.8 (d, 1H), 7.6 (d, 1H), 3.8 (s, 2H), 3.6 (t, 2H), 2.6 (t,2H), 2.0 (quint, 2H).

To a suspension of potassium tert-butoxide (1.5 g, 13 mmol) in THF (12mL) was added HMPA (1.7 mL, 10 mmol) followed by a solution of sulfide(B) (1.8 g, 6.7 mmol) in THF (3 mL) dropwise. The reaction was allowedto stir at room temperature overnight, followed by concentration andpurification by chromatography (Biotage, 40% EtOAc/hexanes) to furnishcyclized product (C) as an orange oil (230 mg, 15%). ¹H NMR (300 MHz,CDCl₃): δ 8.7 (s, 1H), 8.0 (d, 1H), 7.6 (d, 1H), 4.6 (dd, 1H), 3.2 (m,1H), 3.1 (m, 1H), 2.5 (m, 1H), 2.3 (m, 1H), 2.1-1.9 (m, 2H).

To a solution of sulfide (C) (230 mg, 0.99 mmol) and cyanamide (83 mg,2.0 mmol) in dichloromethane (5 mL) at 0° C. was addediodobenzenediacetate (350 mg, 1.1 mmol) all at once. The reaction wasstirred for 3 hr, then concentrated and the crude product purified bychromatography (chromatotron, 50% acetone/hexanes) to furnish thesulfilimine (D) as an orange oil (150 mg, mixture of diastereomers,56%). ¹H NMR (300 MHz, CDCl₃): δ 8.8 (s, 1H), 7.9 (d, 1H), 7.8 (d, 1H),4.8 (dd, 1H), 3.5 (m, 2H), 2.9-2.7 (m, 2H), 2.6 (m, 1H), 2.3 (m, 1H).

To a solution of mCPBA (80%, 180 mg, 0.82 mmol) in EtOH (3 mL) at 0° C.was added a solution of K₂CO₃ (230 mg, 1.7 mmol) in H₂O (1.5 mL). Thesolution was stirred for 20 min and then a solution of sulfilimine (D)(150 mg, 0.55 mmol) in EtOH (2 mL) was added all at once. The reactionwas stirred at 0° C. for 45 min, after which the solvent was decantedinto a separate flask and concentrated to give a white solid. The solidwas slurried in CHCl₃, filtered, and concentrated to furnish puresulfoximine (3) as a colorless oil (72 mg, 44%). ¹H NMR (300 MHz,CDCl₃): δ (1.5:1 mixture of diastereomers) 8.8 (s, 2H), 8.0 (d, 2H), 7.8(d, 2H), 4.7 (q, 1H), 4.6 (q, 1H), 4.0-3.4 (m, s, 4H), 3.0-2.4 (m, 8 H);LC-MS (ELSD): mass calcd for C₁₁H₁₁F₃N₃OS [M+H]⁺ 290.06. Found 289.99.

Example IV[(6-Chloropyridin-3-yl)methyl](methyl)oxido-λ⁴-sulfanylidenecyanamide(4)

[(6-Chloropyridin-3-yl)methyl](methyl)oxido-λ⁴-sulfanylidenecyanamide(4) was prepared from_(—)3-chloromethyl-6-chloropyridine via the same 3step sequence outline in Example I. Product was a white solid;mp=115-117° C; ¹H NMR (300 MHz, CD₃OD/CDCl₃) δ 8.5 (d, 1H), 8.0 (dd,1H), 7.6 (d, 1H), 5.0 (s, 2H), 3.4 (s, 3H); LC-MS (ELSD): mass calcd forC₈H₉ClN₃OS [M+H]⁺ 230. Found 230.

Example V[1-(6-Chloropyridin-3-yl)ethyl](methyl)oxido-λ⁴-sulfanylidenecyanamide(5)

[1-(6-Chloropyridin-3-yl)ethyl](methyl)oxido-λ⁴-sulfanylidenecyanamide(5) was prepared from[(6-chloropyridin-3-yl)methyl](methyl)oxido-λ⁴-sulfanylidenecyanamide(4) via the same protocol as described in Example II. The final product,isolated as a 3:2 mixture of diastereomers, was an off-white solid;mp=155-164° C. LC-MS (ELSD): mass calcd for C₉H₉ClN₃OS [M−H]⁺ 242. Found242. The diastereomers of (5) could be separated by recrystallization(2:1 MeOH/H₂O) and subsequent chromatotron chromatography of thesupernate to provide (6) and (7) (Stereochemistry arbitrarily assigned).

Compound (6) was isolated as a white solid; mp=163-165° C; ¹H NMR (300MHz, CDCl₃): δ 8.4 (d, 1H), 7.9 (dd, 1H), 7.5 (d, 1H), 4.6 (q, 1H), 3.1(s, 3H), 2.0 (d, 3H); LC-MS (ELSD): mass calcd for C₉H₁₁ClN₃OS [M+H]⁺,244. Found 244.

Compound (7) was isolated as a colorless oil; ¹H NMR (300 MHz, CDCl₃) δ8.4 (d, 1H), 7.9 (dd, 1H), 7.5 (d, 1H), 4.6 (q, 1H), 3.0 (s, 3H), 2.0(d, 3H); LC-MS (ELSD): mass calcd for CH₁₁ClN₃OS [M+H]⁺, 244. Found 244.

Example VI 2-(6-Chloropyridin-3-yl)-1-oxido-tetrahydro-1H-1λ⁴-thien-1-ylidenecyanamide (8)

2-(6-Chloropyridin-3-yl)-1-oxido-tetrahydro-1H-1λ⁴-thien-1-ylidenecyanamide (8) was prepared from3-chloromethyl-6-chloropyridine according to the same five step sequencedescribed in Example III. Product was a colorless gum and a 1:1 ratio ofdiastereomers. Diastereomer 1: IR (film) 3439, 3006, 2949, 2194 cm⁻¹; ¹HNMR (300 MHz, CDCl₃): δ 8.4 (d, 1H), 7.8 (dd, 1H), 7.4 (d, 1H), 4.6 (dd,1H), 3.6 (m, 2H), 2.4-2.7 (m, 4H); GC-MS: mass calcd for C₁₀H₁₁ClN₃OS[M+H]⁺ 256. Found 256. Diastereomer 2: IR (film) 3040, 2926, 2191 cm⁻¹;¹H NMR (300 MHz, CDCl₃): δ 8.4 (d, 1H), 7.8 (dd, 1H), 7.4 (d, 1H), 4.7(dd, 1H), 3.8 (ddd, 1H), 3.4 (m, 1H), 2.8 (m, 1H), 2.6 (m, 2H), 2.3 (m,1H); GC-MS: mass calcd for C₁₀H₁₁ClN₃OS [M+H]⁺ 256. Found 256.

Insecticidal Test on Green Peach Aphid (Myzus persicae) Using Mixturesof Sulfoximines and Selected Pesticides

Dose-response, foliar spray assays were designed and conducted toevaluate synergic effects of mixtures between the following compounds

spinosad, spinetoram, gamma-cyhalothrin, methoxyfenozide, orchlorpyrifos, on green peach aphid.

Assay 1: Master solutions at 1000 ppm were made by dissolving technicalmaterials in acetone:MeOH (1:1) at 1 mg/ml. For a mixture between twotest compounds, 0.047 ml of the master solution from each component werecombined and diluted 32× with the acetone:MeOH solvent (0.094 ml ofcombination+2.906 ml solvents, resulting in 15.6 ppm for each ai) andthen 5× with 0.025% Tween 20 in H2O (12 ml) to obtain a 3.125 ppmsolution. For non-mixtures, the master solutions were diluted 64× withacetone:MeOH (0.047 ml+2.953 ml solvent, resulting in 15.6 ppm) and then5× with 0.025% Tween 20 in H2O (12 ml) to obtain a 3.125 ppm solution.For both Mixture and non-mixture, lower concentrations (0.78, 0.195,0.049 and 0.012 ppm) were prepared by sequentially diluting 4 ml of thehigher concentration (starting from 3.125 ppm) with 12 ml of a diluentconsisting 80 parts of 0.025% Tween 20 in H2O and 20 parts ofacetone:MeOH.

Assay 2: Master solutions at 1000 ppm were made by dissolving technicalmaterials in acetone:MeOH (1:1) at 1 mg/ml. For mixtures between Comp 2and Comp 3, 4 or 5, 0.047 ml of the master solution from each componentwere combined and diluted 32× with acetone:MeOH (0.094 ml ofcombination+2.906 ml, resulting in 15.6 ppm for each ai) and then 5×with 0.025% Tween 20 in H2O (12 ml) to obtain a 3.125 ppm solution. Formixtures between Comp 2 and Comp 6 or 7, 0.047 ml of the master solutionfrom Comp 2 and 0.752 ml of the master solution from Comp 6 or 7 werecombined and diluted 3.755× with acetone:MeOH (0.799 ml ofcombination+2.201 ml solvent, resulting in 15.6 ppm for Comp 2 and 250ppm for Comp 6 or 7 ) and then 5× with 0.025% Tween 20 in H2O (12 ml) toobtain a 3.125 ppm solution for Comp 2 and a 50 ppm solution for Comp 6or 7. For non-mixtures with Comp 2, 3, 4 or 5, the master solutions werediluted 64× with acetone:MeOH (0.047 ml+2.953 ml solvent, resulting in15.6 ppm) and then 5× with 0.025% Tween 20 in H2O (12 ml) to obtain a3.125 ppm solution. For non-mixtures with Comp 6 or 7, the mastersolutions were diluted 3.989× with acetone: MeOH (0.752 ml+2.248 mlsolvent, resulting in 250 ppm) and then 5× with 0.025% Tween 20 in H2O(12 ml) to obtain a 50 ppm solution. For both Mixture and non-mixture,lower concentrations (0.78, 0.195, 0.049 and 0.012 ppm for Comp 2,3, 4and 5; 12.5, 3.125, 0.78 and 0.195 for Comp 6 and 7) were prepared bysequentially diluting 4 ml of the higher rate (starting from 3.125 or 50ppm) with 12 ml of a diluent consisting 80 parts of 0.025% Tween 20 inH2O and 20 parts of acetone:MeOH (1:1).

For both Assays 1 and 2, cabbage seedlings grown in 3-inch pots, with2-3 small (3-5 cm) true leaves, were used as test substrate. Theseedlings were infested with 20-50 green peach aphids (wingless adultand nymph) 1 day prior to chemical application. Four seedlings were usedfor each treatment. A hand-held Devilbiss sprayer was used for sprayinga solution to both sides of cabbage leaves until runoff. Referenceplants (solvent check) were sprayed with the diluent only. Treatedplants were held in a holding room for three days at approximately 23°C. and 40% RH prior to grading. Evaluation was conducted by counting thenumber of live aphids per plant under a microscope. Insecticidalactivity was measured by using Abbott's correction formula: Corrected %Control=100*(X−Y)/X where X=No. of live aphids on solvent check plantsY=No. of live aphids on treated plants.

TABLE 1 Results % Control of green peach Test conc, aphid ppm MeasuredPredicted from Compound A Compound B Com A Com B combination Colbycalculation* 1 Spinosad 0.01 0.01 35.71 0.00 1 Spinosad 0.78 0.78 37.500.00 1 Spinosad 0.20 0.20 40.18 0.00 1 Spinosad 0.78 0.78 69.64 49.55 1Spinosad 3.13 3.13 93.75 76.83 1 Spinetoram 0.01 0.01 25.45 0.00 1Spinetoram 0.78 0.78 32.14 0.00 1 Spinetoram 0.20 0.20 33.93 0.00 1Spinetoram 0.78 0.78 69.20 64.73 1 gamma- 0.20 0.20 50.00 0.00cyhalothrin 1 gamma- 0.78 0.78 83.04 79.20 cyhalothrin 1 Methoxyfenozide3.13 3.13 100.00 75.89 1 Chlorpyrifos 0.78 0.78 73.66 49.55 1Chlorpyrifos 3.13 3.13 94.64 75.89 2 Spinosad 0.20 0.20 85.91 69.55 2Spinosad 0.78 0.78 100.00 98.18 2 Spinetoram 0.20 0.20 76.36 69.55 2gamma- 0.78 0.78 100.00 99.77 cyhalothrin 2 Methoxyfenozide 0.05 0.7843.18 0.00 2 Methoxyfenozide 0.20 3.13 76.36 69.55 *Colby Formula = 100− ((100 − % control of compound A) × (100 − % control of compound2))/100 (Colby, S. R. 1967. Calculating synergistic and antagonisticresponses of herbicide combinations. Weeds 15: 20-22)

Acid & Salt Derivatives, and Solvates

The compounds disclosed in this invention can be in the form ofpesticidally acceptable acid addition salts.

By way of non-limiting example, an amine function can form salts withhydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic,citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartaric,lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic,methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, andhydroxyethanesulfonic, acids.

Additionally, by way of non-limiting example, an acid function can formsalts including those derived from alkali or alkaline earth metals andthose derived from ammonia and amines. Examples of preferred cationsinclude sodium, potassium, magnesium, and aminium cations.

The salts are prepared by contacting the free base form with asufficient amount of the desired acid to produce a salt. The free baseforms may be regenerated by treating the salt with a suitable diluteaqueous base solution such as dilute aqueous NaOH, potassium carbonate,ammonia, and sodium bicarbonate.

As an example, in many cases, a pesticide is modified to a more watersoluble form e.g. 2,4-dichlorophenoxy acetic acid dimethyl amine salt isa more water soluble form of 2,4-dichlorophenoxy acetic acid a wellknown herbicide.

The compounds disclosed in this invention can also form stable complexeswith solvent molecules that remain intact after the non-complexedsolvent molecules are removed from the compounds. These complexes areoften referred to as “solvates”.

Stereoisomers

Certain compounds disclosed in this invention can exist as one or morestereoisomers. The various stereoisomers include geometric isomers,diastereomers, and enantiomers. Thus, the compounds disclosed in thisinvention include racemic mixtures, individual stereoisomers, andoptically active mixtures.

It will be appreciated by those skilled in the art that one stereoisomermay be more active than the others. Individual stereoisomers andoptically active mixtures may be obtained by selective syntheticprocedures, by conventional synthetic procedures using resolved startingmaterials, or by conventional resolution procedures.

Pests

In another embodiment, the invention disclosed in this document can beused to control pests.

In another embodiment, the invention disclosed in this document can beused to control pests of the Phylum Nematoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Phylum Arthropoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Chelicerata.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Arachnida.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Myriapoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Symphyla.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Hexapoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Insecta.

In another embodiment, the invention disclosed in this document can beused to control Coleoptera (beetles). A non-exhaustive list of thesepests includes, but is not limited to, Acanthoscelides spp. (weevils),Acanthoscelides obtectus (common bean weevil), Agrilus planipennis(emerald ash borer), Agriotes spp. (wireworms), Anoplophora glabripennis(Asian longhorned beetle), Anthonomus spp. (weevils), Anthonomus grandis(boll weevil), Aphidius spp., Apion spp. (weevils), Apogonia spp.(grubs), Ataenius spretulus (Black Turgrass Ataenius), Atomaria linearis(pygmy mangold beetle), Aulacophore spp., Bothynoderes punctiventris(beet root weevil), Bruchus spp. (weevils), Bruchus pisorum (peaweevil), Cacoesia spp., Callosobruchus maculatus (southern cow peaweevil), Carpophilus hemipteras (dried fruit beetle), Cassida vittata,Cerosterna spp, Cerotoma spp. (chrysomeids), Cerotoma trifurcata (beanleaf beetle), Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis(cabbage seedpod weevil), Ceutorhynchus napi (cabbage curculio),Chaetocnema spp. (chrysomelids), Colaspis spp. (soil beetles), Conoderusscalaris, Conoderus stigmosus, Conotrachelus nenuphar (plum curculio),Cotinus nitidis (Green June beetle), Crioceris asparagi (asparagusbeetle), Cryptolestes ferrugineus (rusty grain beetle), Cryptolestespusillus (flat grain beetle), Cryptolestes turcicus (Turkish grainbeetle), Ctenicera spp. (wireworms), Curculio spp. (weevils),Cyclocephala spp. (grubs), Cylindrocpturus adspersus (sunflower stemweevil), Deporaus marginatus (mango leaf-cutting weevil), Dermesteslardarius (larder beetle), Dermestes maculates (hide beetle), Diabroticaspp. (chrysolemids), Epilachna varivestis (Mexican bean beetle),Faustinus cubae, Hylobius pales (pales weevil), Hypera spp. (weevils),Hypera postica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys futscus, Liogenys suturalis,Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothedgrain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabana, Phyllotreta spp.(chrysomelids), Phynchites spp., Popillia japonica (Japanese beetle),Prostephanus truncates (larger grain borer), Rhizopertha dominica(lesser grain borer), Rhizotrogus spp. (Eurpoean chafer), Rhynchophorusspp. (weevils), Scolytus spp. (wood beetles), Shenophorus spp.(Billbug), Sitona lineatus (pea leaf weevil), Sitophilus spp. (grainweevils), Sitophilus granaries (granary weevil), Sitophilus oryzae (riceweevil), Stegobium paniceum (drugstore beetle), Tribolium spp. (flourbeetles), Tribolium castaneum (red flour beetle), Tribolium confusum(confused flour beetle), Trogoderma variabile (warehouse beetle), andZabrus tenebioides.

In another embodiment, the invention disclosed in this document can beused to control Dermaptera (earwigs).

In another embodiment, the invention disclosed in this document can beused to control Dictyoptera (cockroaches). A non-exhaustive list ofthese pests includes, but is not limited to, Blattella germanica (Germancockroach), Blatta orientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaaustraloasiae (Australian cockroach), Periplaneta brunnea (browncockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In another embodiment, the invention disclosed in this document can beused to control Diptera (true flies). A non-exhaustive list of thesepests includes, but is not limited to, Aedes spp. (mosquitoes), Agromyzafrontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner flies),Anastrepha spp. (fruit flies), Anastrepha suspensa (Caribbean fruitfly), Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies),Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (oriental fruitfly), Ceratitis spp. (fruit flies), Ceratitis capitata (Mediterraneafruit fly), Chrysops spp. (deer flies), Cocliliomyia spp. (screwworms),Contarinia spp. (Gall midges), Culex spp. (mosquitoes), Dasineura spp.(gall midges), Dasineura brassicae (cabbage gall midge), Delia spp.,Delia platura (seedcorn maggot), Drosophila spp. (vinegar flies), Fanniaspp. (filth flies), Fannia canicularis (little house fly), Fanniascalaris (latrine fly), Gasterophilus intestinalis (horse bot fly),Gracillia perseae, Haematobia irritans (horn fly), Hylemyia spp. (rootmaggots), Hypoderma lineatum (common cattle grub), Liriomyza spp.(leafminer flies), Liriomyza brassica (serpentine leafminer), Melophagusovinus (sheep ked), Musca spp. (muscid flies), Musca autumnalis (facefly), Musca domestica (house fly), Oestrus ovis (sheep bot fly),Oscinella frit (frit fly), Pegomyia betae (beet leafminer), Phorbiaspp., Psila rosae (carrot rust fly), Rhagoletis cerasi (cherry fruitfly), Rhagoletis pomonella (apple maggot), Sitodiplosis mosellana(orange wheat blossom midge), Stomoxys calcitrans (stable fly), Tabanusspp. (horse flies), and Tipula spp. (crane flies).

In another embodiment, the invention disclosed in this document can beused to control Hemiptera (true bugs). A non-exhaustive list of thesepests includes, but is not limited to, Acrosternum hilare (green stinkbug), Blissus leucopterus (chinch bug), Calocoris norvegicus (potatomirid), Cimex hemipterus (tropical bed bug), Cimex lectularius (bedbug), Dagbertus fasciatus, Dichelops furcatus, Dysdercus suturellus(cotton stainer), Edessa meditabunda, Eurygaster maura (cereal bug),Euschistus heros, Euschistus servus (brown stink bug), Helopeltisantonii, Helopeltis theivora (tea blight plantbug), Lagynotomus spp.(stink bugs), Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp.(plant bugs), Lygus hesperus (western tarnished plant bug),Maconellicoccus hirsutus, Neurocolpus longirostris, Nezara viridula(southern green stink bug), Phytocoris spp. (plant bugs), Phytocoriscalifornicus, Phytocoris relativus, Piezodorus guildingi, Poecilocapsuslineatus (fourlined plant bug), Psallus vaccinicola, Pseudacystaperseae, Scaptocoris castanea, and Triatoma spp. (bloodsucking conenosebugs/kissing bugs).

In another embodiment, the invention disclosed in this document can beused to control Homoptera (aphids, scales, whiteflies, leafhoppers). Anon-exhaustive list of these pests includes, but is not limited to,Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodesproletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixusfloccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutellabigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii(California red scale), Aphis spp. (aphids), Aphis gossypii (cottonaphid), Aphis pomi (apple aphid), Aulacorthum solani (foxglove aphid),Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia tabaci(sweetpotato whitefly), Brachycolus noxius (Russian aphid),Brachycorynella asparagi (asparagus aphid), Brevennia rehi, Brevicorynebrassicae (cabbage aphid), Ceroplastes spp. (scales), Ceroplastes rubens(red wax scale), Chionaspis spp. (scales), Chrysomphalus spp. (scales),Coccus spp. (scales), Dysaphis plantaginea (rosy apple aphid), Empoascaspp. (leafhoppers), Eriosoma lanigerum (woolly apple aphid), Iceryapurchasi (cottony cushion scale), Idioscopus nitidulus (mangoleafhopper), Laodelphax striatellus (smaller brown planthopper),Lepidosaphes spp., Macrosiphum spp., Macrosiphum euphorbiae (potatoaphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosae(rose aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarvafrimbiolata, Metopolophium dirhodum (rose grain aphid), Mictislongicornis, Myzus persicae (green peach aphid), Nephotettix spp.(leafhoppers), Nephotettix cinctipes (green leafhopper), Nilaparvatalugens (brown planthopper), Parlatoria pergandii (chaff scale),Parlatoria ziziphi (ebony scale), Peregrinus maidis (corn delphacid),Philaenus spp. (spittlebugs), Phylloxera vitifoliae (grape phylloxera),Physokermes piceae (spruce bud scale), Planococcus spp. (mealybugs),Pseudococcus spp. (mealybugs), Pseudococcus brevipes (pine applemealybug), Quadraspidiotus perniciosus (San Jose scale), Rhapalosiphumspp. (aphids), Rhapalosiphum maida (corn leaf aphid), Rhapalosiphum padi(oat bird-cherry aphid), Saissetia spp. (scales), Saissetia oleae (blackscale), Schizaphis graminum (greenbug), Sitobion avenae (English grainaphid), Sogatella furcifera (white-backed planthopper), Therioaphis spp.(aphids), Toumeyella spp. (scales), Toxoptera spp. (aphids),Trialeurodes spp. (whiteflies), Trialeurodes vaporariorum (greenhousewhitefly), Trialeurodes abutiloneus (bandedwing whitefly), Unaspis spp.(scales), Unaspis yanonensis (arrowhead scale), and Zulia entreriana.

In another embodiment, the invention disclosed in this document can beused to control Hymenoptera (ants, wasps, and bees). A non-exhaustivelist of these pests includes, but is not limited to, Acromyrrmex spp.,Athalia rosae, Atta spp. (leafcutting ants), Camponotus spp. (carpenterants), Diprion spp. (sawflies), Formica spp. (ants), Iridomyrmex humilis(Argentine ant), Monomorium ssp., Monomorium minumum (little black ant),Monomorium pharaonis (Pharaoh ant), Neodiprion spp. (sawflies),Pogonomyrmex spp. (harvester ants), Polistes spp. (paper wasps),Solenopsis spp. (fire ants), Tapoinoma sessile (odorous house ant),Tetranomorium spp. (pavement ants), Vespula spp. (yellow jackets), andXylocopa spp. (carpenter bees).

In another embodiment, the invention disclosed in this document can beused to control Isoptera (termites). A non-exhaustive list of thesepests includes, but is not limited to, Coptotennes spp., Coptotermescurvignathus, Coptotermes frenchii, Coptotermes formosanus (Formosansubterranean termite), Cornitennes spp. (nasute termites), Cryptotennesspp. (drywood termites), Heterotermes spp. (desert subterraneantermites), Heterotermes aureus, Kalotermes spp. (drywood termites),Incistitermes spp. (drywood termites), Macrotennes spp. (fungus growingtermites), Marginitermes spp. (drywood termites), Microcerotermes spp.(harvester termites), Microtermes obesi, Procornitermes spp.,Reticulitermes spp. (subterranean termites), Reticulitermes banyulensis,Reticulitermes grassei, Reticulitermes flavipes (eastern subterraneantermite), Reticulitermes hageni, Reticulitermes hesperus (westernsubterranean termite), Reticulitermes santonensis, Reticulitermessperatus, Reticulitermes tibialis, Reticulitermes virginicus,Schedorhinotermes spp., and Zootermopsis spp. (rotten-wood termites).

In another embodiment, the invention disclosed in this document can beused to control Lepidoptera (moths and butterflies). A non-exhaustivelist of these pests includes, but is not limited to, Achoea janata,Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotisipsilon (black cutworm), Alabama argillacea (cotton leafworm), Amorbiacuneana, Amyelosis transitella (navel orangeworm), Anacamptodesdefectaria, Anarsia lineatella (peach twig borer), Anomis sabulifera(jute looper), Anticarsia gemmatalis (velvetbean caterpillar), Archipsargyrospila (fruittree leafroller), Archips rosana (rose leaf roller),Argyrotaenia spp. (tortricid moths), Argyrotaenia citrana (orangetortrix), Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaffolder), Bucculatrix thurberiella (cotton leafperforator), Caloptiliaspp. (leaf miners), Capua reticulana, Carposina niponensis (peach fruitmoth), Chilo spp., Chlumetia transversa (mango shoot borer),Choristoneura rosaceana (obliquebanded leafroller), Chrysodeixis spp.,Cnaphalocerus medinalis (grass leafroller), Colias spp., Conpomorphacramerella, Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydia funebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),Diatraea saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Earias insulata(Egyptian bollworm), Earias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma saucia (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarpa, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophagaincertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), andZeuzera pyrina (leopard moth).

In another embodiment, the invention disclosed in this document can beused to control Mallophaga (chewing lice). A non-exhaustive list ofthese pests includes, but is not limited to, Bovicola ovis (sheep bitinglouse), Menacanthus stramineus (chicken body louse), and Menopongallinea (common hen house).

In another embodiment, the invention disclosed in this document can beused to control Orthoptera (grasshoppers, locusts, and crickets). Anon-exhaustive list of these pests includes, but is not limited to,Anabrus simplex (Mormon cricket), Gryllotalpidae (mole crickets),Locusta migratoria, Melanoplus spp. (grasshoppers), Microcentrumretinerve (angularwinged katydid), Pterophylla spp. (kaydids),chistocerca gregaria, Scudderia furcata (forktailed bush katydid), andValanga nigricorni.

In another embodiment, the invention disclosed in this document can beused to control Phthiraptera (sucking lice). A non-exhaustive list ofthese pests includes, but is not limited to, Haematopinus spp. (cattleand hog lice), Linognathus ovillus (sheep louse), Pediculus humanuscapitis (human body louse), Pediculus humanus humanus (human body lice),and Pthirus pubis (crab louse),

In another embodiment, the invention disclosed in this document can beused to control Siphonaptera (fleas). A non-exhaustive list of thesepests includes, but is not limited to, Ctenocephalides canis (dog flea),Ctenocephalides felis (cat flea), and Pulex irritans (human flea).

In another embodiment, the invention disclosed in this document can beused to control Thysanoptera (thrips). A non-exhaustive list of thesepests includes, but is not limited to, Frankliniella fusca (tobaccothrips), Frankliniella occidentalis (western flower thrips),Frankliniella shultzei Frankliniella williamsi (corn thrips),Heliothrips haemorrhaidalis (greenhouse thrips), Riphiphorothripscruentatus, Scirtothrips spp., Scirtothrips citri (citrus thrips),Scirtothrips dorsalis (yellow tea thrips), Taeniothripsrhopalantennalis, and Thrips spp.

In another embodiment, the invention disclosed in this document can beused to control Thysanura (bristletails). A non-exhaustive list of thesepests includes, but is not limited to, Lepisma spp. (silverfish) andThermobia spp. (firebrats).

In another embodiment, the invention disclosed in this document can beused to control Acarina (mites and ticks). A non-exhaustive list ofthese pests includes, but is not limited to, Acarapsis woodi (trachealmite of honeybees), Acarus spp. (food mites), Acarus siro (grain mite),Aceria mangiferae (mango bud mite), Aculops spp., Aculops lycopersici(tomato russet mite), Aculops pelekasi, Aculus pelekassi, Aculusschlechtendali (apple rust mite), Amblyomma americanum (lone star tick),Boophilus spp. (ticks), Brevipalpus obovatus (privet mite), Brevipalpusphoenicis (red and black flat mite), Demodex spp. (mange mites),Dermacentor spp. (hard ticks), Dermacentor variabilis (american dogtick), Dermatophagoides pteronyssinus (house dust mite), Eotetranycusspp., Eotetranychus carpini (yellow spider mite), Epitimerus spp.,Eriophyes spp., Ixodes spp. (ticks), Metatetranycus spp., Notoedrescati, Oligonychus spp., Oligonychus coffee, Oligonychus ilicus (southernred mite), Panonychus spp., Panonychus citri (citrus red mite),Panonychus ulmi (European red mite), Phyllocoptruta oleivora (citrusrust mite), Polyphagotarsonemun latus (broad mite), Rhipicephalussanguineus (brown dog tick), Rhizoglyphus spp. (bulb mites), Sarcoptesscabiei (itch mite), Tegolophus perseaflorae, Tetranychus spp.,Tetranychus urticae (twospotted spider mite), and Varroa destructor(honey bee mite).

In another embodiment, the invention disclosed in this document can beused to control Nematoda (nematodes). A non-exhaustive list of thesepests includes, but is not limited to, Aphelenchoides spp. (bud and leaf& pine wood nematodes), Belonolaimus spp. (sting nematodes),Criconemella spp. (ring nematodes), Dirofilaria immitis (dog heartwom),Ditylenchus spp. (stem and bulb nematodes), Heterodera spp. (cystnematodes), Heterodera zeae (corn cyst nematode), Hirschmanniella spp.(root nematodes), Hoplolaimus spp. (lance nematodes), Meloidogyne spp.(root knot nematodes), Meloidogyne incognita (root knot nematode),Onchocerca volvulus (hook-tail worm), Pratylenchus spp. (lesionnematodes), Radopholus spp. (burrowing nematodes), and Rotylenchusreniformis (kidney-shaped nematode).

In another embodiment, the invention disclosed in this document can beused to control Symphyla (symphylans). A non-exhaustive list of thesepests includes, but is not limited to, Scutigerella immaculata.

For more detailed information consult “Handbook of Pest Control—TheBehavior, Life Histroy, and Control of Household Pests” by ArnoldMallis, 9^(th) Edition, copyright 2004 by GIE Media Inc.

Mixtures

Some of the pesticides that can be employed beneficially in combinationwith the invention disclosed in this document include, but are notlimited to the following:

1,2 dichloropropane, 1,3 dichloropropene,

abamectin, acephate, acequinocyl, acetamiprid, acethion, acetoprole,acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin,allethrin, allosamidin, allyxycarb, alpha cypermethrin, alpha ecdysone,amidithion, amidoflumet, aminocarb, amiton, amitraz, anabasine, arsenousoxide, athidathion, azadirachtin, azamethiphos, azinphos ethyl, azinphosmethyl, azobenzene, azocyclotin, azothoate,

barium hexafluorosilicate, barthrin, benclothiaz, bendiocarb,benfuracarb, benomyl, benoxafos, bensultap, benzoximate, benzylbenzoate, beta cyfluthrin, beta cypermethrin, bifenazate, bifenthrin,binapacryl, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron,borax, boric acid, bromfenvinfos, bromo DDT, bromocyclen, bromophos,bromophos ethyl, bromopropylate, bufencarb, buprofezin, butacarb,butathiofos, butocarboxim, butonate, butoxycarboxim,

cadusafos, calcium arsenate, calcium polysulfide, camphechlor,carbanolate, carbaryl, carbofuran, carbon disulfide, carbontetrachloride, carbophenothion, carbosulfan, cartap, chinomethionat,chlorantraniliprole, chlorbenside, chlorbicyclen, chlordane,chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenethol,chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfluazuron,chlormephos, chlorobenzilate, chloroform, chloromebuform,chloromethiuron, chloropicrin, chloropropylate, chlorphoxim,chlorprazophos, chlorpyrifos, chlorpyrifos methyl, chlorthiophos,chromafenozide, cinerin I, cinerin II, cismethrin, cloethocarb,clofentezine, closantel, clothianidin, copper acetoarsenite, copperarsenate, copper naphthenate, copper oleate, coumaphos, coumithoate,crotamiton, crotoxyphos, cruentaren A&B, crufomate, cryolite,cyanofenphos, cyanophos, cyanthoate, cyclethrin, cycloprothrin,cyenopyrafen, cyflumetofen, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyphenothrin, cyromazine, cythioate,

d-limonene, dazomet, DBCP, DCIP, DDT, decarbofuran, deltamethrin,demephion, demephion O, demephion S, demeton, demeton methyl, demeton O,demeton O methyl, demeton S, demeton S methyl, demeton S methylsulphon,diafenthiuron, dialifos, diamidafos, diazinon, dicapthon,dichlofenthion, dichlofluanid, dichlorvos, dicofol, dicresyl,dicrotophos, dicyclanil, dieldrin, dienochlor, diflovidazin,diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate,dimethrin, dimethylvinphos, dimetilan, dinex, dinobuton, dinocap,dinocap 4, dinocap 6, dinocton, dinopenton, dinoprop, dinosam,dinosulfon, dinotefuran, dinoterbon, diofenolan, dioxabenzofos,dioxacarb, dioxathion, diphenyl sulfone, disulfiram, disulfoton,dithicrofos, DNOC, dofenapyn, doramectin,

ecdysterone, emamectin, EMPC, empenthrin, endosulfan, endothion, endrin,EPN, epofenonane, eprinomectin, esfenvalerate, etaphos, ethiofencarb,ethion, ethiprole, ethoate methyl, ethoprophos, ethyl DDD, ethylformate, ethylene dibromide, ethylene dichloride, ethylene oxide,etofenprox, etoxazole, etrimfos, EXD,

famphur, fenamiphos, fenazaflor, fenazaquin, fenbutatin oxide,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenothiocarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin,fenpyroximate, fenson, fensulfothion, fenthion, fenthion ethyl,fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron,flubendiamide, flubenzimine, flucofuron, flucycloxuron, flucythrinate,fluenetil, flufenerim, flufenoxuron, flufenprox, flumethrin,fluorbenside, fluvalinate, fonofos, formetanate, formothion,formparanate, fosmethilan, fospirate, fosthiazate, fosthietan,fosthietan, furathiocarb, furethrin, furfural,

gamma cyhalothrin, gamma HCH,

halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos,heterophos, hexaflumuron, hexythiazox, HHDN, hydramethylnon, hydrogencyanide, hydroprene, hyquincarb,

imicyafos, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP,isamidofos, isazofos, isobenzan, isocarbophos, isodrin, isofenphos,isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin

jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenilehormone II, juvenile hormone III,

kelevan, kinoprene,

lambda cyhalothrin, lead arsenate, lepimectin, leptophos, lindane,lirimfos, lufenuron, lythidathion,

malathion, malonoben, mazidox, mecarbam, mecarphon, menazon,mephosfolan, mercurous chloride, mesulfen, mesulfenfos, metaflumizone,metam, methacrifos, methamidophos, methidathion, methiocarb,methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide,methyl bromide, methyl isothiocyanate, methylchloroform, methylenechloride, metofluthrin, metolcarb, metoxadiazone, mevinphos,mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, MNAF,monocrotophos, morphothion, moxidectin,

naftalofos, naled, naphthalene, nicotine, nifluridide, nikkomycins,nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron,

omethoate, oxamyl, oxydemeton methyl, oxydeprofos, oxydisulfoton,

paradichlorobenzene, parathion, parathion methyl, penfluron,pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate,phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon,phosphine, phosphocarb, phoxim, phoxim methyl, pirimetaphos, pirimicarb,pirimiphos ethyl, pirimiphos methyl, potassium arsenite, potassiumthiocyanate, pp′ DDT, prallethrin, precocene I, precocene II, precoceneIII, primidophos, proclonol, profenofos, profluthrin, promacyl,promecarb, propaphos, propargite, propetamphos, propoxur, prothidathion,prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole,pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyridaben,pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate,pyriprole, pyriproxyfen,

quassia, quinalphos, quinalphos, quinalphos methyl, quinothion,quantifies,

rafoxanide, resmethrin, rotenone, ryania,

sabadilla, schradan, selamectin, silafluofen, sodium arsenite, sodiumfluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulcofuron, sulfiram, sulfluramid, sulfotep, sulfur, sulfuryl fluoride,sulprofos,

tau fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad,tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin,terbufos, tetrachloroethane, tetrachlorvinphos, tetradifon,tetramethrin, tetranactin, tetrasul, theta cypermethrin, thiacloprid,thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb,thiofanox, thiometon, thionazin, thioquinox, thiosultap, thuringiensin,tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene,triazamate, triazophos, trichlorfon, trichlormetaphos 3, trichloronat,trifenofos, triflumuron, trimethacarb, triprene,

vamidothion, vamidothion, vaniliprole, vaniliprole,

XMC, xylylcarb,

zeta cypermethrin and zolaprofos.

Additionally, any combination of the above pesticides can be used.

The invention disclosed in this document can also be used withherbicides and fungicides, both for reasons of economy and synergy.

The invention disclosed in this document can be used withantimicrobials, bactericides, defoliants, safeners, synergists,algaecides, attractants, desiccants, pheromones, repellants, animaldips, avicides, disinfectants, semiochemicals, and molluscicides (thesecategories not necessarily mutually exclusive) for reasons of economy,and synergy.

For more information consult “Compendium of Pesticide Common Names”located at http://www.alanwood.net/pesticides/index.html as of thefiling date of this document. Also consult “The Pesticide Manual”14^(th) Edition, edited by C D S Tomlin, copyright 2006 by British CropProduction Council.

Synergistic Mixtures

The invention disclosed in this document can be used with othercompounds such as the ones mentioned under the heading “Mixtures” toform synergistic mixtures where the mode of action of the compounds inthe mixtures are the same, similar, or different.

Examples of mode of actions include, but are not limited to: acetylcholine esterase inhibitor; sodium channel modulator; chitinbiosynthesis inhibitor; GABA-gated chloride channel antagonist; GABA andglutamate-gated chloride channel agonist; acetyl choline receptoragonist; MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinicacetylcholine receptor; Midgut membrane disrupter; and oxidativephosphorylation disrupter.

Additionally, the following compounds are known as synergists and can beused with the invention disclosed in this document: piperonyl butoxide,piprotal, propyl isome, sesamex, sesamolin, and sulfoxide.

Formulations

A pesticide is rarely suitable for application in its pure form. It isusually necessary to add other substances so that the pesticide can beused at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticide activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra low volume solutions.

For further information on formulation types see “Catalogue of pesticideformulation types and international coding system” Technical Monographn^(o)2, 5^(th) Edition by CropLife International (2002).

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations, areeither solids, usually known as wettable powders, or water dispersiblegranules, or liquids usually known as emulsifiable concentrates, oraqueous suspensions. Wettable powders, which may be compacted to formwater dispersible granules, comprise an intimate mixture of thepesticide, a carrier, and surfactants. The concentration of thepesticide is usually from about 10% to about 90% by weight. The carrieris usually chosen from among the attapulgite clays, the montmorilloniteclays, the diatomaceous earths, or the purified silicates. Effectivesurfactants, comprising from about 0.5% to about 10% of the wettablepowder, are found among sulfonated lignins, condensednaphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates,alkyl sulfates, and nonionic surfactants such as ethylene oxide adductsof alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are chosen from conventionalanionic and nonionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums, may also be added, to increase the densityand viscosity of the aqueous carrier. It is often most effective togrind and mix the pesticide at the same time by preparing the aqueousmixture and homogenizing it in an implement such as a sand mill, ballmill, or piston-type homogenizer.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier which has beenpre-formed to the appropriate particle size, in the range of from about0.5 to 3 mm. Such compositions may also be formulated by making a doughor paste of the carrier and compound and crushing and drying to obtainthe desired granular particle size.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. They canbe applied as a seed dressing, or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. They are use in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings or in special chambers.

Pesticides can be microencapsulated by suspending the pesticideparticles or droplets in plastic polymers of various types. By alteringthe chemistry of the polymer or by changing factors in the processing,microcapsules can be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which. inturn, affects the residual performance, speed of action, and odor of theproduct.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one compound which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers. Further information onthe embodiment is disclosed in U.S. patent publication 20070027034published Feb. 1, 2007, having Patent Application Ser. No. 11/495,228.For ease of use this embodiment will be referred to as For furtherinformation consult “Insect Pest Management” 2^(nd) Edition by D. Dent,copyright CAB International (2000). Additionally, for more detailedinformation consult “Handbook of Pest Control—The Behavior, LifeHistroy, and Control of Household Pests” by Arnold Mallis, 9^(th)Edition, copyright 2004 by GIE Media Inc.

Other Formulation Components

Generally, the invention disclosed in this document when used in aformulation, such formulation can also contain other components. Thesecomponents include, but are not limited to, (this is a non-exhaustiveand non-mutually exclusive list) wetters, spreaders, stickers,penetrants, buffers, sequestering agents, drift reduction agents,compatibility agents, anti-foam agents, cleaning agents, andemulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulphate;sodium dioctyl sulphosuccinate; alkyl phenol ethoxylates; and aliphaticalcohol ethoxylates.

A dispersing agent is a substance which adsorbs onto the surface of aparticles and helps to preserve the state of dispersion of the particlesand prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulphonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such as sodium naphthalene sulphonate formaldehydecondensates. Tristyrylphenol ethoxylate phosphate esters are also used.Non-ionics such as alkylarylethylene oxide condensates and EO-PO blockcopolymers are sometimes combined with anionics as dispersing agents forsuspension concentrates, In recent years, new types of very highmolecular weight polymeric surfactants have been developed as dispersingagents. These have very long hydrophobic ‘backbones’ and a large numberof ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.These high molecular weight polymers can give very good long-termstability to suspension concentrates because the hydrophobic backboneshave many anchoring points onto the particle surfaces. Examples ofdispersing agents used in agrochemical formulations are: sodiumlignosulphonates; sodium naphthalene sulphonate formaldehydecondensates; tristyrylphenol ethoxylate phosphate esters; aliphaticalcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graftcopolymers.

An emulsifying agent is a substance which stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends containalkylphenol or aliphatic alcohol with 12 or more ethylene oxide unitsand the oil-soluble calcium salt of dodecylbenzene sulphonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from 8 to 18 willnormally provide good stable emulsions. Emulsion stability can sometimesbe improved by the addition of a small amount of an EO-PO blockcopolymer surfactant.

A solubilizing agent is a surfactant which will form micelles in waterat concentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilized water-insoluble materialsinside the hydrophobic part of the micelle. The type of surfactantsusually used for solubilization are non-ionics: sorbitan monooleates;sorbitan monooleate ethoxylates; and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alky ethoxylates; linear aliphatic alcoholethoxylates; aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersarc usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, ULV formulations, and to a lesser extent granularformulations. Sometimes mixtures of solvents are used. The first maingroups of solvents are aliphatic paraffinic oils such as kerosene orrefined paraffins. The second main group and the most common comprisesthe aromatic solvents such as xylene and higher molecular weightfractions of C₉ and C₁₀ aromatic solvents. Chlorinated hydrocarbons areuseful as cosolvents to prevent crystallization of pesticides when theformulation is emulsified into water. Alcohols are sometimes used ascosolvents to increase solvent power.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, emulsions and suspoemulsions to modify therheology or flow properties of the liquid and to prevent separation andsettling of the dispersed particles or droplets. Thickening, gelling,and anti-settling agents generally fall into two categories, namelywater-insoluble particulates and water-soluble polymers. It is possibleto produce suspension concentrate formulations using clays and silicas.Examples of these types of materials, include, but are limited to,montmorillonite, e.g. bentonite; magnesium aluminum silicate; andattapulgite. Water-soluble polysaccharides have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds or aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum; locust bean gum; carrageenam;alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC);hydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms which cause spoilage of formulated products. Thereforepreservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are limited to. propionic acid andits sodium salt; sorbic acid and its sodium or potassium salts; benzoicacid and its sodium salt; p-hydroxy benzoic acid sodium salt; methylp-hydroxy benzoate; and 1,2-benzisothiazalin-3-one (BIT).

The presence of surfactants, which lower interfacial tension, oftencauses water-based formulations to foam during mixing operations inproduction and in application through a spray tank. In order to reducethe tendency to foam, anti-foam agents are often added either during theproduction stage or before filling into bottles. Generally, there aretwo types of anti-foam agents, namely silicones and non-silicones.Silicones are usually aqueous emulsions of dimethyl polysiloxane whilethe non-silicone anti-foam agents are water-insoluble oils, such asoctanol and nonanol, or silica. In both cases, the function of theanti-foam agent is to displace the surfactant from the air-waterinterface.

For further information see “Chemistry and Technology of AgrochemicalFormulations” edited by D. A. Knowles, copyright 1998 by Kluwer AcademicPublishers. Also see “Insecticides in Agriculture andEnvironment—Retrospects and Prospects” by A. S. Perry, I. Yamamoto, I.Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.

Applications

The actual amount of pesticide to be applied to loci of pests is notcritical and can readily be determined by those skilled in the art. Ingeneral, concentrations from about 0.01 grams of pesticide per hectareto about 5000 grams of pesticide per hectare are expected to providegood control.

The locus to which a pesticide is applied can be any locus inhabited byan pest, for example, vegetable crops, fruit and nut trees, grape vines,ornamental plants, domesticated animals, the interior or exteriorsurfaces of buildings, and the soil around buildings.

Generally, with baits, the baits are placed in the ground where, forexample, termites can come into contact with the bait. Baits can also beapplied to a surface of a building, (horizontal, vertical, or slant,surface) where, for example, ants, termites, cockroaches, and flies, cancome into contact with the bait.

Because of the unique ability of the eggs of some pests to resistpesticides repeated applications may be desirable to control newlyemerged larvae.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying the pesticides to adifferent portion of the plant. For example, control of foliar-feedinginsects can be controlled by drip irrigation or furrow application, orby treating the seed before planting. Seed treatment can be applied toall types of seeds, including those from which plants geneticallytransformed to express specialized traits will germinate. Representativeexamples include those expressing proteins toxic to invertebrate pests,such as Bacillus thuringiensis or other insecticidal toxins, thoseexpressing herbicide resistance, such as “Roundup Ready” seed, or thosewith “stacked” foreign genes expressing insecticidal toxins, herbicideresistance, nutrition-enhancement or any other beneficial traits.Furthermore, such seed treatments with the invention disclosed in thisdocument can further enhance the ability of a plant to better withstandstressful growing conditions. This results in a healthier, more vigorousplant, which can lead to higher yields at harvest time.

The invention disclosed in this document is suitable for controllingendoparasites and ectoparasites in the veterinary medicine sector or inthe field of animal keeping. Compounds according to the invention areapplied here in a known manner, such as by oral administration in theform of, for example, tablets, capsules, drinks, granules, by dermalapplication in the form of, for example, dipping, spraying, pouring on,spotting on, and dusting, and by parenteral administration in the formof, for example, an injection.

The invention disclosed in this document can also be employedadvantageously in livestock keeping, for example, cattle, sheep, pigs,chickens, and geese. Suitable formulations are administered orally tothe animals with the drinking water or feed. The dosages andformulations that are suitable depend on the species.

The invention disclosed in this document can also be used Before apesticide can be used or sold commercially, such pesticide undergoeslengthy evaluation processes by various governmental authorities (local,regional, state, national, international). Voluminous data requirementsare specified by regulatory authorities and must be addressed throughdata generation and submission by the product registrant or by anotheron the product registrant's behalf. These governmental authorities thenreview such data and if a determination of safety is concluded, providethe potential user or seller with product registration approval.Thereafter, in that locality where the product registration is grantedand supported, such user or seller may use or sell such pesticide.

The headings in this document are for convenience only and must not beused to interpret any portion thereof.

1. A composition comprising (a)

wherein X represents NO₂, CN or COOR⁴; L represents a single bond or R¹,S and L taken together represent a 5- or 6-membered ring; R¹ representsmethyl or ethyl; R² and R³ independently represent hydrogen, methyl,ethyl, fluoro, chloro or bromo; n is an integer from 0-3; Y represents6-halopyridin-3-yl, 6-(C₁-C₄)alkylpyridin-3-yl,6-halo(C₁-C₄)alkylpyridin-3-yl, 6-(C₁-C₄)alkoxypyridin-3-yl,6-halo(C₁-C₄)alkoxypyridin-3-yl, 2-chlorothiazol-4-yl, or3-chloroisoxazol-5-yl when n=0-3 and L represents a single bond, or Yrepresents hydrogen, C₁-C₄ alkyl, phenyl, 6-halopyridin-3-yl,6-(C₁-C₄)alkylpyridin-3-yl, 6-halo(C₁-C₄)alkylpyridin-3-yl,6-(C₁-C₄)alkoxypyridin-3-yl, 6-halo(C₁-C₄)alkoxypyridin-3-yl,2-chlorothiazol-4-yl, or 3-chloroisoxazol-5-yl when n=0-1 and R¹, S andL taken together represent a 5- or 6-membered ring; and R⁴ representsC₁-C₃ alkyl; and (b) at least one other pesticide.
 2. A compositionaccording to claim 1 wherein (a) is

and (b) is spinosad, spinetoram, gamma-cyhalothrin, methoxyfenozide,chlorpyrifos, or a mixture thereof.
 3. A process comprising applying acomposition according to claim 1 to a locus to control pests.
 4. Aprocess of applying a composition of claim 1 to a seed.
 5. A process ofapplying a composition of claim 1 to a seed that has been geneticallytransformed to express one or more specialized traits.
 6. A process ofapplying a composition of claim 1 to a genetically transformed plantthat has been genetically transformed to express one or more specializedtraits.
 7. A process of orally administering or applying a compositionof claim 1 to an animal.
 8. A process comprising submitting datarelating to a composition of claim 1 to a governmental authority inorder to obtain product registration approval for a product comprising acomposition of claim 1.